This is very subjective, and I would close ... but i'd like to hear other answers.
When working on a web-app, without the luxury of a designer ... I probably spend about 10% of my time on the CSS, with a KISS attitude. If I wanted, I could spend hours getting the design perfect, but that should be done after the coding.
What I tend to do is ensure 100% separation of the design. Sometimes, using a JSON/XML based API to contain the entire business logic, and the 'usable site' just backs onto that internally with authorization. This way, the web app/site is just a client of a private API. Then, hours can be spent on design later providing the API remains consistent. It also helps with the asyc UI components to wrap everything in an API you can expose to the client.
I like doing design as much as the coding, I just find the return on time invested is smaller when fiddling with CSS, so put it off for that reason. I do however think that the UX and design is the most important part of a website or app.